Photographic developers



United States Patent 3,134,673 PHOTOGRAPHIC DEVELOPERS Karl ()tto Gauguin, Stoclrport, David William Crichton Ramsay, Sale, and Albert Edward Kaye, Middleton, England, assignors to Ilford Limited, Ilford, Essex, England, a British company No Drawing. Filed Feb. 10, 1961, Ser. No. 88,317 Claims priority, application Great Britain Feb. 19, 1960 1 Claim. (Cl. 96-66) This invention relates to photographic developer compositions, i.e. compositions suitable for use in the development of silver halide photographic emulsions.

According to the present invention there are provided photographic developing compositions which comprise, in association with an alkaline substance, a compound of the general Formula I:

or a salt or anil thereof, where R is an alkyl group containing 1 to 6 carbon atoms, R is a methyl, ethyl, hydroxymethyl or hydroxyethyl group, or R and R together with the nitrogen atom to which they are joined constitute a pyrrolidine or piperidine nucleus, or one of R and R is a trimethylene grouping of which the free valency is connected to the carbon atom of the benzene ring which is in ortho position to the nitrogen atom and the other ofR and R has any of the meanings assigned individually to R and R above or is a hydrogen atom, and X is an alkyl group containing 1 or 2 carbon atoms or an alkoxy or substituted alkoxy group containing 1 to 6 carbon atoms or, where R or R forms part of a cyclic residue, is either a said alkyl, or alkoxy or substituted alkoxy group or a hydrogen atom.

Preferred compounds of the general Formula I are those in which the sum total number of carbon atoms in the groups R and R whether joined together or not, is at most four.

Preferred classes of compounds according to the present invention are:

(a) Those in which R is alkyl of 1-6 carbon atoms, R is methyl, ethyl, hydroxymethyl or hydroxyethyl, and X is methyl, methoxy, ethoxy or ,B-hydroxye-thoxy.

([1) Those in which represents a pyrrolidine or piperidine nucleus and X is methyl, methoxy, ethoxy or ,B-hydroxyethoxy.

(0) Those of the tetrahydroquinolic type having the formula:

R-NCH;,

I OH

where R is hydrogen or methyl and X is hydrogen.

In accordance with a preferred form of this invention the developing compositions contain, in addition to an alkaline substance and a compound of general Formula I, a proportion of hydroquinone.

3,134,673 Patented May 26, 1964 The compounds of general Formula I have been found to be very powerful developer substances which produce super-additivity in black and white and colour developer compositions. In black and white developer compositions of the conventional metol-hydroquinone types they can be used as substitutes for the metol at weight concentrations as low as 15 to 20% of the Weight concentration of metol, the resulting developers being at least as powerful as the conventional compositions with the additional advantages of greater economies, less toxicity and superior keeping qualities.

The developing compounds of general Formula I can be used in association with other developing substances, apart from hydroquinone just mentioned, e.g. hydroquinone monosulphonate, phenyl glycine, ascorbic acid and reductones, pyrogallol and gentisic acid.

The invention further includes colour developing compositions which contain, in addition to a compound of general Formula I and an alkaline substance, a developing substance based on N.N-dialkyl p-phenylene diamine and derivatives thereof, e.g. the toluene analogues. In this connection the compounds of general Formula I tend to increase the activity of the developers. It is a particularly important advantage of the compounds, however, that when present in such colour developing compositions which also contain colour couplers which tend to oxidise in the air, their presence, even in minor proportions, acts to minimise or inhibit such oxidation, i.e. developers thus formulated have a reduced tendency to the formationof a dye scum, in use or on keeping.

As already indicated, the developing compositions may contain either compounds of general Formula I per se or salts or anils thereof.

Compounds of the general Formula I may be made, for example, by the following processes:

(1) By treating an amino compound of the general Formula H:

with an oxidising agent, e.g. ferric chloride, thereby to replace the amino group by a hydroxyl group.

This process may conveniently be carried out as follows:

The compoiuid II is dissolved in water containing sufiicient acid to form a salt at temperature, e.g. between 15 and C., and an aqueous solution of between 0.1 and 0.2 mol. proportions of ferric chloride is added. The reaction proceeds at room temperature but may be boiled to speed up the reaction and allowed to cool to room temperature. The developer product may then be extracted from the reaction mixture by known methods such as crystallisation or solvent extraction.

(2) By alkylating or hydroxyalkylating a compound of the general Formula III:

llvH, (III) X (in 0 thereby to introduce the groups R and R This process 3 ethyl bromide, 1:4-dibromobutane or ethylene chlorohydrin.

The following are exemplary procedures for the production of compounds of the aforesaid general Formula I:

DEVELOPER A 4-Hydr0xy-3-Methyl-N:N-Diethylaniline Hemisulphate A mixture of 42.5 parts of 4-diethylarnino-Z-methylaniline, 23 parts of sulphuric acid and 25 parts of water is heated to 80 C. and a solution of 14 parts of ferric chloride in 25 parts of water added all at once with vigorous stirring. The reaction mixture is finally heated under reflux for minutes and then allowed to cool to room temperature. Addition of 200 parts of ethanol precipitates a non-developing product which is rejected. The filtrates are brought to pH 7 with caustic liquor and extracted with 500 parts of trichloroethylene. The extract is shaken with a solution of 12.5 parts of sulphuric acid in 200 parts of water. The aqueous layer is separated, concentrated to half volume and cooled. The product is collected, washed with ethanol and crystallised from water. 4-hydroxy-3-methyl N:N diethylaniline hemisulphate separates as colourless prisms, which melt with decomposition at between 256 C. and 258 C. On analysis the product is found to contain 57.6% of carbon and 7.5% of hydrogen. C11H17ON1/2H2SO4 requires 58.0% of carbon and 7.9% of hydrogen.

DEVELOPER B 4-Hydr0xy-3-Metlzyl-N-ethyl-N-B-Hydroxyethyl Aniline Naphthalene-1:5-Disulph0nate (2:1 Salt) A mixture of 48 parts of 4-arnino-3-methyl-N-ethyl-N- B-hydroxyethyl aniline naphthalene-1:5-disulphonate (1:1 salt) and 50 parts of Water is heated to 80 C. and a solution of 6 parts of ferric chloride in 6 parts of water added all at once with vigorous stirring. The reaction mixture is finally heated under reflux for 15 minutes and then allowed to cool by standing overnight. The product is collected, washed with ethanol and crystallized from Water. The product separates as colourless prisms which melt with decomposition at between 230 C. and 232 C. On analysis the product is found to contain 56.4% of carbon, 6.0% of hydrogen and 9.9% of sulphur.

requires 56.6% of carbon, 6.2% of hydrogen and 9.5% of sulphur.

DEVELOPER C N-(4'-Hydr0xy-3'-Methylphenyl) Pyrralidine-Naphthalene 1:5-Disulph0nate (2:1 Salt) A mixture of parts of 4-amino-2-methyl-phenol and 43 parts of 1:4-dibromobutane is stirred and heated to 40 C. The internal temperature then rises to 110 C. due to the exothermic reaction. The reaction mixture is finally stirred for 1 hour at 95 C. After cooling to 60 C. the melt is dissolved in a mixture of 36 parts of hydrochloric acid and 240 parts of water and the whole extracted with 600 parts of chloroform. The aqueous layer is separated and neutralised with sodium bicarbonate. The product is collected, washed with water, dried over phosphorus pentoxide, then crystallised from petroleum ether (B. Pt. 6080 C.). N-(4'-hydroxy-3-methylphenyl)-pyrrolidine separates as colourless needles which melt at between 84 C. and 85 C. On analysis the product is found to contain 74.7% of carbon and 8.6% of hydrogen. C H ON requires 74.6% of carbon and 8.5% of hydrogen. The naphthalene-1:S-disulphonate (2:1 salt) of N-(4'-hydroxy-3-methylphenyl)pyrrolidine separates from water as colourless prisms which melt with decomposition at 272 C. On analysis the product is found to contain 59.6% of carbon, 5.9% of hydI'OgBD. and Of I'lltI'OgCIl. C11H15ON1/2C10H3O6S2 requires 59.8% of carbon, 5.9% of hydrogen and 4.4% of nitrogen.

4 DEVELOPER D 4-Hydroxy-3-Methyl-N :N-Dimethylaniline-Naphthalene- 1:5-Disulph0nate (2:1 Salt) In place of the 48 parts of 4-amino-3-methyl-N-ethyl- N-fi-hydroxyethylaniline naphthalene 1:5 disulphonate 1:1 salt) used in making Developer B, there are used 44 parts of 4-amino-3-methyl-N:N-dimethylaniline naphthalene-1:5-disulphonate (1:1 salt). The 4-hydroxy-3- methyl N:N dimethylaniline naphthalene-lzS-disulphonate (2:1 salt) so obtained separates from ethanol as colourless prisms which melt with decomposition at between 266 C. and 268 C.

On analysis the product is found to contain 57.1% of carbon and 5.8% of hydrogen. C H ON /2C H O S requires 56.9% of carbon and 5.8% of hydrogen.

DEVELOPER E 4-Hydr0xy-3-Methyl-N-n-B utyl-N-fl-Hydroxyethylaniline Naphthalene-1 :5 -Dz'sul phonate (2 :1 Salt) In place of the 48 parts of 4-amino-3-methyl-N-ethyl- N-fl-hydroxyethylaniline naphthalene 1:5 disulphonate (1:1 salt) used in making Developer B, there are used 52 parts of 4-amino-3-methyl-N-n-butyl-N-B-hydroxyethylaniline naphthalene-1:S-disulphonate (1:1 salt) and in place of 6 parts of ferric chloride there are used 5 parts of potassium persulphate. The 4-hydroxy-3-methyl-N- n-butyl-N-fi-hydroxyethylaniline naphthalene-1 5 -disulphonate (2:1 salt) so obtained separates from water as colourless prisms which melt with decomposition at 214 C.

On analysis the product is found to contain 59.1% of carbon, 6.6% of hydrogen and 3.7% of nitrogen.

C13H21O2N1/2C10H8O6S2 requires 58.9% of carbon, 6.8% of hydrogen and 3.8% of nitrogen.

DEVELOPER F 4 -H ydroxy-3-M ethyl-N -n-H exyl-N -(3-H ydroxyethylaniline Naphthalene-1:5-Disulph0nate (2:1 Salt) In place of 48 parts of 4-amino-3-methyl-N-ethyl-N-/3- hydroxyethylaniline naphthalene-1:5-disulphonate (1:1 salt) used in making Developer B, there are used 54 parts of 4-amino-3-rnethyl-N-n-heXyl-N-,B-hydroxyethylaniline naphthalene-1:S-disulphonate (1:1 salt) and in place of 6 parts of ferric chloride there are used 6 parts of potassium persulphate. The 4-hydroxy-3-methyl-N- n-p-hydroxyethylaniline naphthalene 1:5 disulphonate (2:1 salt) so obtained separates from water as colourless prisms which melt with decomposition at between 178 C. and 180 C.

On analysis the product is found to contain 60.9% of carbon, 7.2% of hydrogen and 3.6% of nitrogen.

C15H25O2N1/2C10H8O6S2 requires 60.8% of carbon, 7.3% of hydrogen and 3.5% of nitrogen.

DEVELOPER G 4-Hydroxy-3-Methoxy-N:N-Diethylaniline Naphthalene- 1:5-Disalph0nate (2 :1 Salt) In place of the 48 parts of 4-amino-3-methyl-N-ethyl- N-fl-hydroxyethylaniline naphthalene 1:5 disulphonate (1:1 salt) used in making Developer B, there are used 48 parts of 4-amino-3-methoxy-N:N-diethylaniline naphthalene-1:5-disulphonate (1:1 salt) and in place of 6 parts there are used 9 parts of ferric chloride. The 4-hydroxy- 3-methoxy-N:N-diethylaniline naphthalene-1 5 -disulphonate (2:1 salt) so obtained separates from water as colourless prisms which melt with decomposition at between 277 C. and 278 C.

On analysis the product is found to contain 56.4% of carbon, 6.3% of hydrogen and 4.0% of nitrogen.

requires 56.6% of carbon, 6.2% of hydrogen and 4.1% of nitrogen.

DEVELOPER H N-(4 '-H ydroxy-3'-M ethyl phenyl -Piperidine Hydrobromide A mixture of 25 parts of 4-hydroxy-3-methylaniline and 46 parts of pentamethylene dibromide in 500 parts of dry xylene is boiled under reflux for 6 hours. After standing overnight the solid so obtained is filtered off and crystallised from water. N-(4'-hydroxy-3'-methylphen yl)-piperidine hydrobromide separates as colourless needles which melt with decomposition at 250 C.

On analysis the product is found to contain 53.1% of carbon, 6.3% of hydrogen and 4.6% of nitrogen. C H ONJ-llBr requires 53.0% of carbon, 6.6% of hydrogen and 5.1% of nitrogen.

DEVELOPER I 6-Hydr0xy-1-Methyl-l :2 :3 :4-Tetrahydr0quinoline Naphthalene-1 :5-D'isulph0nate (2:1 Salt) A mixture of 57 parts of 6-hydroxyquinoline methiodide, 4 par-ts of triethylamine and 100 parts of formic acid is boiled under reflux rfior hours. After cooling to room temperature the reaction mixture is neutralised by the addition of sodium hydrogen carbonate and extracted exhaustively with chloroform. The combined extracts are shaken with a solution of 55 parts of naphthalene-1:5- di-sulphonic acid in 500 parts of water. The solid which separates is collected and recrystallised from water. 6- hydroxy 1 methyl-1:2:3:4-tetrahydroquinoline naphthalene-lzS-disulphonate (2:1 salt) separates as prisms which melt with decomposition at 300 C.

On analysis the product is found to contain 58.7% of carbon 5.3% of hydrogen and 4.6% of nitrogen. C H ON /2C H O S requires 58.6% of carbon, 5.5% of hydrogen and 4.6% of nitrogen.

DEVELOPER I 4-Hydr0xy-3-(B-Hydroxyethoxy) -N :N-Diethylaniline Naphthalene-1 :5-Disulph0nate (2 :1 Salt) In place of the 48 parts of 4-amino-3-methyl-N-ethyl N ,8 hydroxyethylaniline naphthalene-1:S-disulphonate (1 :1 salt) used in making Developer B, there are used 51 parts of 4-amino-3-(fi-hydroxyethoxy)-N:N-diethylaniline naphthalene-1:S-disulphonate (1:1 salt) and in place of 6 parts of ferric chloride there are used 6 parts of potassium persulphate. 'Ihe 4-hydroxy-3-(,B-hydroxyethoxy)- N:N diethylaniline naphthalene-1:S-disulphonate (2:1 salt) so obtained separates from water as colourless prisms which melt with decomposition at 232 C.

On analysis the product is found to contain 55.3% of carbon and 6.0% of hydrogen. C H O N /2C H O S requires 55.3% of carbon and 6.2% of hydrogen.

The following examples will serve to illustrate the invention:

Example 1 Identical strips of a high speed black and White panchromatic negative film material (sold under the trade name Ilford HP3, the Word Ilford being a registered trademark) are exposed behind a sensitometric step wedge and equal numbers are then developed for different times in the following two developer solutions:

Parts by weight Metol Sodium sulphite, anhydrous 75 Hydroquinone 8 Sodium carbonate, anhydrous 37.5 Potassium bromide 2 Water to make 3000 4 hydroxy-3-methyl-N:N-diethylaniline hemisulphate 0.274 Sodium sulphite, anhydrous 75 Hydroqninone 8 Sodium carbonate, anhydrous 37.5 Potassium bromide 2 Water to make 3000 The developed strips are treated in a stop bath, fixed and washed in conventional manner.

The processed step wedges are measured and the densit-ies plotted individually for each development time.

The high supe-radditive efiiciency of the compound used in the developer compositions of the present invention is apparent.

Example 2 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.386 part of N- (4 hydroxy-3'-methylphenyl)-pyrrolidine naphthalene- 1:5-disulphonate (2:1 salt) is incorporated in solution (b).

The high superadditive efliciency of the compound used in the developer compositions of the present invention is shown.

Example 3 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.179 part of 6- hydroxy-lz2z3z4-tetrahydroquinoline is incorporated in solution (b).

The high superadditive efficiency of the compound used in the developer compositions of the present invention is shown.

Example 4 The compound 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate was added in a proportion of 1 g./litre to a cyan colour developer which in the absence of said addition commenced to develop dye scum almost immediately after making. By the addition of the said compound the onset of dye scum was prevented for 36 hours.

Example 5 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.441 part of 4- :hydroxy 3 methyl-N-n-butyl-N 3-hyd-roxyethylaniline naphthalene-1:S-disulphona-te (2:1 salt) is incorporated in solution (b).

Example 6 In place 'of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.475 part of 4- hydroxy 3 methyl-N-n-hexyl-N-p-hydroxyethylaniline naphthalene-1:S-disulphonate (2:1 salt) is incorporated in solution (b).

Example 7 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.407 part of 4- hydroxy-3-methoxy-N:N-diethylaniline naphthalene-1 :5 disulphonate (2:1 salt) is incorporated in solution (b).

Example 8 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.327 part of N- (4-hydroxy-3-methy1phenyl) piperidine hydrobromide is incorporated in solution (b).

Example 9 In place of 0.274 part of 4-hydroxy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.370 part of 6- hydroxy 1 methyl-1z2z3z4-tetrahydroquinoline naphthalene-1:5-disulphonate (2:1 salt) is incorporated in solution (b).

7 Example 10 In place of 0.274 part of 4-hydroXy-3-methyl-N:N-diethylaniline hemisulphate in Example 1, 0.444 part of 4- hydroxy-B-(B-hydroxyethoXweN:N-diethylaniline naphthalene-lzS-disulphonate (2:1 salt) is incorporated in solution (b).

What we claim is:

A photographic developing composition comprising an alkaline substance, hydroquinone and a salt of N-(4'-hydroxy-3-methylphenyl)pyrrolidine.

8 References Cited in the file of this patent UNITED STATES PATENTS 1,937,844 Reed Dec. 5, 1933 5 2,417,514 Neumann Mar. 18, 1947 2,943,109 Ramsay June 28, 1960 OTHER REFERENCES Mees: The Theory of the Photographic Process, rev. ed., The Macmillan Co., New York, 1954, pages 546, 10 552, 56365. 

